Sulfoximine-containing detergent compositions



, dation to non-surface active sulfones.

laundering process.

3,255,116 SULFOXIMINE-CONTAINING DETERGENT COMPOSITIONS Jim S. Berry, Cincinnati, Ohio, assignor to The Procter &

Gamble Company, Cincinnati, Ohio, a corporation of Ohio N Drawing. Original application Dec. 26, 1962, Ser. Divided and this application Oct. 16,

No. 247,314. 1964, Ser. No. 404,501

7 Claims. (Cl. 252-95) This patent application is a divisional patent application of Serial Number 247,314 filed on December 26, 1962 by Jim S. Berry, and now abandoned.

This invention relates to a novel class of organic sulfur containing detergent compounds. More especially this invention relates to unsymmetrical sulfoximine compounds which are valuable detergent surfactants and to detergency compositions containing such compounds.

There are several properties that are regarded as being essential for a compound to be suitable for use as a detergent surfactant. Foremost, of course, is the cleaning ability or ability to remove soil from soiled clothes. In addition, the detergent surfactant should remain in an active form under conditions of usage including high temperatures and aqueous solutions. It is also advantageous for an active detergent material to be compatable with the many adjuvants and additives that are frequently incorporated into detergent formulations, including bleaches and other oxidizing media.

The novel sulfoximine compounds of this invention have been discovered to be thermally stable and resistant to hydrolysis in basic solutions. Furthermore, sulfoximine compounds of this invention are resistant to further oxidation, unlike the somewhat related sulfoxide detergents which show a propensity to undergo further oxi- Thus unlike the sulfoxides, the novel sulfoximine compounds of this invention can be used advantageously in detergent formulations containing peroxygen bleaches, or in other oxidizing media.

Bleaching agents, for example those of the peroxygen type, are often used in connection with detergents in the Occasionally in household situations a consumer will add a bleaching agent to a washing solution to aid in the cleaning process. This can easily result in the unintentional inactivation of the detergent compound unless the detergent compound is resistant to such bleaching agents. It is clearly an advantage therefore to have a detergent active that can be used along with such bleaching agents without themselves being transformed into an inactive form.

It is a principal object of this invention to provide as a novel class of organic detergents unsymmetrical sulfoximine detergent compounds which have good detergency, thermal stability, stability against hydrolysis in basic solutions, and which are resistant to further oxidation in the presence of peroxygen bleaches.

It is also an object of this invention to provide improved detergency compositions containing these new compounds.

It was found that these and other objects are achieved by a novel class of sulfur containing compounds having the structure set forth below and by detergent compositions containing such compounds as hereinafter more fully described.

The novel sulfoximine compounds of this invention have the following formula:

United States Patent 0 3,255,116 Patented June 7, 1966 ICC wherein R is an aliphatic radical selected from the group consisting of straight chain, branched chain, saturated and unsaturated alkyl and alkenyl radicals having from 10 to about 18 carbon atoms, and wherein R is an alkyl radical selected from the group consisting of methyl and ethyl radicals.

The above formula depicts the sulfur-oxygen bond and the sulfur-nitrogen bond as being of a semi-polar nature, and is thus depicted as a convenient way of representation. It is recognized that other ways of representing the actual bonding are used and may be equally suitable.

The long chain aliphatic substituent as defined above can be a straight chain, branched chain, saturated or unsaturated aliphatic radical having from 10 to about 18 carbon atoms. Examples are given hereinafter. The long chain aliphatic substituent can suitably be obtained from synthetic or natural sources such as coconut oil fatty alcohol which contains a mixture of alkyl and alkenyl radicals having predominantly a carbon chain length within the prescribed range.

Examples of sulfoximine detergent compounds provided -by this invention include the following: decyl methyl sulfoximine, dodecyl methyl sulfoximine, tetradecyl methyl sulfoximine, octadecyl methyl sulfoximine, decyl ethyl sulfoximine, dodecyl ethyl sulfoximine, tetradecyl ethyl sulfoximine, hexadeeyl ethyl sulfoximine, octadecyl ethyl sulfoximine, 2-methyl undecyl methyl sulfoximine, tetrapropylene methyl sulfoximine, dodecenyl methyl sulfoximine and tetradecenyl ethyl sulfoximine.

Short chain sulfoximine compounds are known in the prior art. It has never been recognized heretofore, however, that the particular unsymmetrical sulfoximine compounds of this invention have the highly desirable properties for use as detergents in the manner previously set forth.

According to this invention, the sulfoximine compounds which have the necessary properties to be good detergent compounds are those which can be termed unsymmetrical sulfoximines. By unsymmetrical is meant those sulfoximines in which one aliphatic group is quite long with respect to the other. Preferably, the short alkyl group should contain no more than two carbon atoms, while the long alkyl chain should contain ten or more carbon atoms. If less than ten carbons are present in the long chain aliphatic hydrocarbon radical, cleaning effectiveness of the compound is seriously impaired. In order for the molecule to possess cleaning power, the higher aliphatic radical must contain more than ten carbon atoms, e.g. to 10 to 18 or 20 carbon atoms.

The most preferred unsymmetrical sulfoximine compounds are the C -C alkyl methyl sulfoximines. Particularly desirable are the C -C alkyl methyl sulfoximine compounds.

The synthesis of the members of the new class of unsymmetrical sulfoximine compounds of this invention is illustrated by the following examples.

EXAMPLE I To 23.2 g. (0.10 mole) dodecyl methyl sulfoxide dissolved in 250 ml. chloroform was added, dropwise with stirring, 30 ml. concentrated sulfuric acid. Temperature was maintained at 25-30 C. during addition. Sodium azide (13.0 g., 0.20 mole) was added in small portions with stirring over a period of 30 minutes, keeping the reaction temperature at 30-32 C. After stirring at room temperature 1 /2 hours, the temperature was raised to 35 C. and stirring continued for 20 hours. The reaction mixture, after several water washings was cooled in an acetone-Dry Ice bath and filtered. The filter cake, methyldodecylsulfoximinium sulfate, weighed about 21 g. (71% yield). It was purified by recrystallization from acetone-ethanol or chloroformhexane, to M.P. 128-30.

3 Excellent analyses were obtained for the sulfate salt. (Calcd. for [C H SO(NH )CH SO,: C=52.7%; H=10.2%; S=l6.2% N=4.73%. Found: C=52.7%; H=l0.2%; S=16.9%; N=4.70%.)

The crude filter cake was dissolved in 300 ml. hot ethanol and 100 ml. ethanol containing 3.2 g. NaOH was added. The mixture was filtered through a Celite filter pad. The clear filtrate was chilled in an acetone-Dry Ice bath and filtered. After two recrystallizations from acetone the dodecyl methyl sulfoximine product melted at 60 C. and weighed 13.3 g. (overall yield from sulfoxide =54%). (Calcd. for C H SO(NH)CH C=63.2%; H=l1.7%; S=12.9%; N=5.67%. Found: C=62.9%; H=11.6%; S=l2.9%; N=5.51%.)

By substituting different starting sulfoxides for the dodecyl methyl sulfoxide of the previous example, homologous members of the novel class of compounds can be prepared. For example when decyl methyl sulfoxide was used, and essentially the same procedure followed, decyl methyl sulfoximine was recovered in a yield of 25.5%. The compound had a melting point of 51 C.

Tetradecyl methyl sulfoximine was prepared according to the previous example by using tetradecyl methyl sulfoxide as a starting material. The compound yield was 61% and the compound had a melting point of 60 C.

The dodecyl, decyl and tetradecyl methyl sulfoximines prepared in the manner described above can be used in detergent compositions as hereinafter described.

Compounds of the invention are useful per se as detergents and surface active agents. Desirably, they are used with other materials to form detergent compositions, as for example, liquid, bar or granular compositions. Such detergent compositions can contain the unsymmetrical sulfoximines of this invention and water-soluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts or mixtures thereof in a ratio of sulfoximine compound to builder salt of about 3:1 to about 1:10. A preferred ratio of sulfoximine to builder is 2:1 to about 1:5.

Granular detergent compositions preferably contain about 5% to about 50% of the sulfoximine compounds of this invention and liquid formulations preferably contain about 2% to about of such sulfoximines. Granular detergent compositions preferably contain at least an equal amount of an alkaline builder salt. Liquid formulations preferably contain from about 5% to about of a water soluble alkaline builder salt, the balance of the composition being a solvent such as water, and/ or other liquid vehicles.

Water-soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametahosphate, sodium sesquicarbonate, sodium monoand di-ortho phosphate and potassium bicarbonate. Potassium pyrophosphate finds wide application especially in built liquid detergent compositions.

Examples of organic alkaline sequestrant builder salts which can be used alone with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)- ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N-(Z-hydroxyethyl)-nitrilo diacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g. sodium phytate are also suitable as organic alkaline sequestrant builder salts (see US. Patent 2,739,942).

The unsymmetrical sulfoximine detergent compounds may be used as the sole detergent agent or they may be mixed with other well known detergent compounds such as anionic and nonionic detergent compounds.

Anionic organic detergents which can be used in the compositions of this invention, if desired, include both the soap and non-soap detergents. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates, alkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionates; acyl N-methyl taurides; alkylbenzenesulfonates; alkyl phenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively, contain 10 to 20 carbon atoms. They are used in the form of water-soluble salts, the sodium, potassium, ammonium, and alkylolammonium salts, for example. Specific examples are: sodium lauryl sulfate; potassium N-methyl lauroyl tauride; triethanolammonium dodecylbenzene sulfonate.

The examples of nonionic organic detergents which can be used in the compositions of this invention if desired are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms (e.g. t-octylphenol and the ethylene oxide is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to 25:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5,000 to 11,000; the condensation products of from 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms (e.g. lauryl alcohol); C -C alkyl di-(C C alkyl) amine oxides (e.g. dodecyl dimethyl amine oxide).

Preferred liquid detergent compositions contain about 2 to about 30% of the sulfoximine compounds of the invention and about 5% to about 40% potassium pyrophosphate. Desirably the G -C alkyl methyl sulfoximines are used in such preferred compositions. Particularly desirable in built liquid compositions is dodecyl methyl sulfoximine.

The detergent compositions of this invention can contain any of the usual adjuvants, diluents and additives, for example, ampholytic, cationic or zwitterionic detergents, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fiuorescers, suds builders, suds depressors and the like, without detracting from the advantageous properties of the composition.

Built laundry detergent compositions containing 50% sodium tripoly-phosphate, 30% sodium sulfate and 20% dodecyl methyl sulfoximine or tetradecyl methyl sulfoximine result in lipid soil detergency properties (using naturally soiled cloth) comparable to like formulations containing sodium dodecylbenzenesulfonate which is a well known detergent compound widely used in commercially available detergency compositions. The same basic formulation, but containing octadecyl methyl sulfoximine, hexadecyl methyl sulfoximine, hexadecyl ethyl sulfoximine or decyl ethyl sulfoximine have satisfactory detergent characteristics but not as desirable as those compositions containing the C and C homologues.

The above-described sulfoximine compounds are efficient solubilizers and dispersers of calcium soap as well as being hydrolytically stable in base solution and resistant to oxidation from peroxygen type bleaches. Examples of peroxygen type bleaches which can be employed with the novel sulfoximine detergent compounds of this invention are sodium perborate, sodium perbenzoate, sodium perlaurate, sodium perazelate, sodium persebacate, peroxyphosphate, peroxycarbonate and Oxone," which is a potassium hydrogen persulfate bleach. These bleaching agents can be incorporated into a detergent composition or be added during the washing cycle. Hydrogen peroxide can also be used during the washing cycle. The peroxygen bleaches may comprise from about 3% to about 15% by weight of the composition and preferably from 5% to about Cleansing and laundering compositions prepared according to this invention which can be used in the usual household laundering situations can contain from about 2% to 50% by weight of the unsymmetrical sulfoximine detergent compounds, 25% to 80% by weight of sodium tripolyphosphate or other previously mentioned builder, 12% to 45% by weight of sodium sulfate, 0% to 15% by weight of sodium silicate and 0% to about 40% by weight of water.

The following examples are presented for illustrative purposes only.

EXAMPLE II Granular detergent: Percent Dodecyl methyl sulfoximine 17.5 Sodium tripolyphosphate 50.0 Sodium silicate 6.0 Sodium sulfate 15.0 Sodium perbenzoate 8.0 Water 3.5

An aqueous solution containing from about .15% to An aqueous solution containing from about 0.15% to 0.45% concentration of the above formula provides effective cleaning results in both laundering and dishwashing situations.

EXAMPLE 111 Granular detergent: Percent Dodecyl methyl sulfoximine 10 Sodium dodecylbenzenesulfonate (the dodecyl group being derived from tetrapropylene) 10 Sodium tripolyphosphate 50 Sodium sulfate 30 EXAMPLE IV Granular detergent: Percent Tetradecyl methyl sulfoximine 10 Condensation product of one mole of nonyl phenol and nine moles of ethylene oxide 10 Sodium pyrophosphate 40 Sodium perborate 10 Sodium carbonate 3 Trisodium phosphate 3 Sodium sulfate 24 EXAMPLE V Liquid detergent: Percent Dodecyl methyl sulfoximine 6 Sodium dodecylbenzenesulfonate 6 Potassium pyrophosphate Potassium toluene sulfonate 8 Sodium silicate 3.8 Carboxymethyl hydroxyethyl cellulose 0.3 Water, balance.

EXAMPLE VI Liquid detergent: Percent Dodecyl methyl sulfoximine l0 Tet-rapotassium ethylenediaminetetraacetate 25 Water 65 6 EXAMPLE VII Liquid detergent: Percent Dodecyl methyl sulfoximine 25 Sodium tripolyphosphate 25 Sodium sulfate 20 Sodium silicate 15 Water 5 Sodium perborate 10 The foregoing description and examples of this invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

What is claimed is:

1. A detergent composition consisting essentially of an unsymmetrical sulfoximine detergent compound having the following general formula:

0 T R-s-R' I l-H wherein R is an aliphatic radical selected from the group consisting of straight or branched chain saturated alkyl radicals having from 10 to about 18 carbon atoms, and wherein R is an alkyl radical selected from the group consisting of methyl and ethyl radicals, and a builder material selected from the group consisting of water-soluble inorganic alkaline builder salts, organic alkaline sequestrant builder salts and mixtures thereof, wherein the ratio of said detergent to said builder is in the range of 3:1 to about 1:10 by weight.

2. The detergent composition of claim 1 wherein the ratio of said detergent to said builder is in the range of 2:1 to about 1:5 by weight.

3. The detergent composition of claim 1 including from about 3% -to about 15% by weight of a peroxygen type bleach selected from the group consisting of sodium per borate, sodium perbenzoate, sodium perlaurate, sodium perazelate, sodium persebacate, peroxyphosphate, peroxycarbonate, and potassium hydrogen persulfate.

4. A laundering and detergent composition consisting essentially of an active detergent compound an unsymmetrical alkyl methyl sulfoximine compound, wherein the alkyl radical contains from 10 to about 18 carbon atoms, and a builder salt selected from the group consisting of water-soluble inorganic alkaline builder salts, organic alkaline sequestrant builder salts and mixtures thereof, the ratio of said detergent compound to said builder salt being in the range of about 3:1 to about 1:10 by weight.

5. The laundering and detergent composition of claim 4 wherein the alkyl radical in said unsymmetrical sulfoxirnine compound ranges in chain length from 12 to 14 carbon atoms.

6. A built liquid detergent composition consisting essentially of from about 2% to about 30% of the unsymmetrical sulfoximine detergent compound having the following general formula:

wherein R is an aliphatic radical selected from the group consisting of straight or branched chain saturated alkyl radicals having from 10 to about 18 carbon atoms, and wherein R' is an alkyl radical selected from the group consisting of methyl and ethyl radicals, from about 5% to about 40% of a builder salt selected from the group consisting of water-soluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts, and mixtures thereof, the balance of the composition being water.

7. The built liquid detergent composition of claim 6 wherein the sulfoximine compound is dodecyl methyl sulfoximine.

References Cited by the Examiner UNITED STATES PATENTS 2,787,595 4/1957 Webb 252-138 2,925,442 2/1960 Goheen et a1. 260607 3,058,916 10/1962 Sinner et a1. 252-99 3,130,165 4/ 1964 Brocklehu-rst 252-99 8 FOREIGN PATENTS 8/1960 Germany.

OTHER REFERENCES Jerchel et a1.: Chem. Ber., volume 87, pages 947-955 (1945).

A New Type Peroxygen Composition Oxone Monopersulfate Compound, Publ. of E. I. du Pont, January 10, 1961, pages 3, 4 and 8.

JULIUS GREENWALD, Primary Examiner.

ALBERT T. MEYERS, Assistant Examiner. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF AN UNSYMMETRICAL SULFOXIMINE DETERGENT COMPOUND HAVING THE FOLLOWING GENERAL FORMULA:
 3. THE DETERGENT COMPOSITION OF CLAIM INCLUDING FROM ABOUT 3% TO ABOUT 15% BY WEIGHT OF PEROXYGEN TYPE BLEACH SELECTED FROM THE GOURP CONSISTING OF SODIUM PERBORATE, SODIUM PERBENZOATE, SODIUM PERLAURATE, SODIUM PERAZELATE, SODIUM PERSEBACATE, PEROXYPHOSPHATE, PEROXYCARBONATE, ADN POTASSIUM HYDROGEN PERSULFATE. 